WO2009080235A1 - Stabilisation vis-à-vis des uv d'une composition de polyoléfine réticulable comprenant un catalyseur acide de condensation des silanols acides - Google Patents

Stabilisation vis-à-vis des uv d'une composition de polyoléfine réticulable comprenant un catalyseur acide de condensation des silanols acides Download PDF

Info

Publication number
WO2009080235A1
WO2009080235A1 PCT/EP2008/010653 EP2008010653W WO2009080235A1 WO 2009080235 A1 WO2009080235 A1 WO 2009080235A1 EP 2008010653 W EP2008010653 W EP 2008010653W WO 2009080235 A1 WO2009080235 A1 WO 2009080235A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin composition
composition according
polyolefin
cross
silanol condensation
Prior art date
Application number
PCT/EP2008/010653
Other languages
English (en)
Inventor
Perry Nylander
Original Assignee
Borealis Technology Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Borealis Technology Oy filed Critical Borealis Technology Oy
Priority to CN2008801217386A priority Critical patent/CN101903451B/zh
Priority to US12/809,569 priority patent/US20100267869A1/en
Priority to BRPI0821163A priority patent/BRPI0821163B1/pt
Publication of WO2009080235A1 publication Critical patent/WO2009080235A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • UV stabilisation of a cross-linkable polyolefin composition comprising an acidic silanol condensation catalyst
  • the present invention relates to a polyolefin composition comprising a cross-linkable polyolefin with hydrolysable silane groups, and an acidic silanol condensation catalyst which shows excellent curing and UV resistance, to an article, in particular a wire or a cable, comprising such a polyolefin composition, and to the use of such a composition for the production of an article, in particular a wire or cable.
  • cross-link polyolefins by means of additives as this improves the properties of the polyolefin such as mechanical strength and chemical heat resistance.
  • Cross-linking may be performed by condensation of silanol groups contained in the polyolefin which can be obtained by hydrolysation of silane groups.
  • a silane compound can be introduced as a cross-linkable group e.g. by grafting the silane compound onto a polyolefin, or by copolymerisation of olefin monomers and silane group containing monomers.
  • Such techniques are known e.g. from US 4,413,066, US 4.297,310, US 4,351 ,876, US 4,397,981 , US 4,446,283 and US 4,456,704.
  • a silanol condensation catalyst For cross-linking of polyolefins, a silanol condensation catalyst must be used.
  • Conventional catalysts are for example tin-organic compounds such as dibutyl tin dilaurate (DBTDL).
  • DBTDL dibutyl tin dilaurate
  • the cross- linking process advantageously is carried out in the presence of acidic silanol condensation catalysts.
  • acidic catalysts allow cross-linking to quickly take place already at room temperature and with no risk to release tin organic compounds to the environment.
  • Such acidic silanol condensation catalysts are disclosed for example in WO 95/17463. The contents of this document is enclosed herein by reference.
  • UV stabilizers typically used in polymer applications in the prior art so that on the one hand protection from damages derived from ultraviolet rays and on the other hand the cure is killed. Therefore, polymer compositions which are cross-linked by acidic silanol condensation catalysts show minor UV resistance and cannot be used for applications where UV resistant formulations are required like installation cables, cable de fasade and outdoor pipes.
  • US 6,337,367 B1 discloses a silane cross-linked insulation material which comprises a substituted benzotriazole as UV stabilizer. However, the cross-linking catalyst is not disclosed.
  • a benzotriazole derivative is used in CN 1500836 A as UV stabilizer in polyolefin compositions used for the production of polycarbonate plastic-wood boards.
  • JP 2003-3192846 A discloses a silane cross-linked polyolefin composition which comprises a benzotriazole derivative as UV stabilizer and a (meth)acrylate-based and/or an allylic cross-linking auxiliary for the use in electric wires.
  • triazoles cannot be used in polymer compositions comprising an acidic silanol condensation catalyst as they would interact with the cross-linking components in an acidic environment.
  • the present application therefore provides a polyolefin composition
  • a polyolefin composition comprising
  • ⁇ F is more than 40 Nm and the cross-linking speed is more than 0.1 Nm/s in the ice test and retention of more than 60% of the elongation at break after 500 h in SEPAP UV exposure.
  • the present invention relates to a polyolefin composition
  • a polyolefin composition comprising
  • (C) at least one UV stabilizer that is acidic, i.e. pH equal or less than 6.2, measured at 20-25 0 C and with 1 wt% suspension.
  • R being a substituted or non-substituted hydrocarbon residue with at least 6 C-atoms
  • R1 to R4 being independently the same or different substituted or non-substituted hydrocarbon residues, hydrogen atoms or hetero atoms,
  • R3 to R6 being independently the same or different hydrocarbon
  • the UV stabilizer according to formula (I) and/or (II) is present in an amount of 5.0 wt% or less, more preferably 2.5 wt% or less, most preferably 1.0 wt% or less.
  • the UV stabilizer (C) has a pH of equal or less than 6.1 , measured at 20-25 0 C and with 1 wt% suspension.
  • the at least one UV stabilizer does not spoil the reactivity with the acidic silanol condensation catalyst. Therefore products comprising the composition show improved protection from UV light combined with good cross- linking properties.
  • At least one UV stabilizer (C) R in formula (I) further comprises at least one aryl group which may be substituted or non-substituted.
  • R in formula (I) preferably further comprises at least 8 C- atoms, more preferably at least 12 C-atoms, most preferably at least 14 C- atoms.
  • FM 1 R2, R3, and R4 are independently hydrogen atoms or halogen atoms.
  • the at least one UV stabilizer (C) may comprise the structural unit according to formula (I) one or several times, e.g. two or three times.
  • two structural units according to formula (I) may be linked to each other via a bridging group.
  • the currently most preferred components of formula (I) are 2- (3, 5-Di- tert- pentyl-2-hydroxyphenyl) benzotriazole (Cas 25973-55-1), 2-(2'-Hydroxy- 5'-tert-octylphenyl) benzotriazole (Cas 3147-75-9), 2-(2 1 -Hydroxy-3',5'-di-t- butylphenyl)-5-chlorobenzotriazole (Cas 3864-99-1 ), 2-(2-Hydroxy-3,5-di- ( ⁇ . ⁇ -dimethylbenzyl)phenyl) 2H-benzotriazole (Cas 70321 -86-7), 2-(3',5'- di-fe/7-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole (Cas 3846-71-7), and 2,2'-methylene-bis(6-(2H-benzotriazo
  • R1 in formula (II) preferably represents hydrocarbon.
  • R3 to R6 represent methyl.
  • the currently most preferred components of formula (II) is Bis(1 - undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)-carbonate (Cas 705257-84- 7).
  • composition of all aspects of the present invention comprises a cross-linkable polyolefin containing hydrolysable silane groups (A).
  • cross-linkable polyolefin comprises, still more preferably consists of, a polyethylene containing hydrolysable silane groups.
  • the hydrolysable silane groups may be introduced into the polyolefin by copolymerisation of e.g. ethylene monomers with silane group containing comonomers or by grafting, i.e. by chemical modification of the polymer by addition of silane groups mostly in a radical reaction. Both techniques are well known in the art.
  • the silane group containing polyolefin has been obtained by copolymerisation.
  • the copolymerisation is preferably carried out with an unsaturated silane compound represented by the formula
  • R 1 is an ethylenically unsaturated hydrocarbyl, hydrocarbyloxy or (meth)acryloxy hydrocarbyl group
  • R 2 is an aliphatic saturated hydrocarbyl group
  • Y which may be the same or different, is a hydrolysable organic group
  • q 0, 1 or 2.
  • the unsaturated silane compound are those wherein R 1 is vinyl, allyl, isopropenyl, butenyl, cyclohexanyl or gamma- (meth)acryloxy propyl; Y is methoxy, ethoxy, formyloxy, acetoxy, propionyloxy or an alkyl- or arylamino group; and R 2 , if present, is a methyl, ethyl, propyl, decyl or phenyl group.
  • a preferred unsaturated silane compound is represented by the formula
  • A is a hydrocarbyl group having 1-8 carbon atoms, preferably 1- 4 carbon atoms.
  • the most preferred compounds are vinyl trimethoxysilane, vinyl bismethoxyethoxysilane, vinyl triethoxysilane, gamma-(meth)acryl- oxypropyl trimethoxysilane, gamma(meth)acryloxypropyl triethoxysilane, and vinyl triacetoxysilane, or combinations of two or more thereof.
  • the copolymerisation of the olefin, e.g. ethylene, and the unsaturated silane compound may be carried out under any suitable conditions resulting in the copolymerisation of the two monomers.
  • the silane group containing polyolefin (A) preferably contains 0.001 to 15 wt. % of the silane group containing monomers, more preferably 0.01 to 5 wt. %, and still more preferably 0.1 to 3 wt.%, and most preferably 0.4 to 2.4 wt.%.
  • composition comprises a polyolefin with polar group containing monomer units.
  • the polar groups are selected from siloxane, amide, anhydride, carboxylic, carbonyl, hydroxyl, ester and epoxy groups.
  • the polar groups may for example be introduced into the polymer by grafting of an ethylene polymer with a polar-group containing compound, i.e. by chemical modification of the polyolefin by addition of a polar group containing compound mostly in a radical reaction. Grafting is e.g. described in US 3,646,155 and US 4,117,195.
  • said polar groups are introduced into the polymer by copolymerisation of olefinic, including ethylene, monomers with comonomers bearing polar groups.
  • comonomers having polar groups may be mentioned the following: (a) vinyl carboxylate esters, such as vinyl acetate and vinyl pivalate, (b) (meth)acrylates, such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate and hydroxyethyl(meth)acrylate,
  • olefinically unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid and fumaric acid
  • (d) (meth)acrylic acid derivatives such as (meth)acrylonitrile and (meth)acrylic amide
  • (e) vinyl ethers such as vinyl methyl ether and vinyl phenyl ether.
  • vinyl esters of monocarboxylic acids having 1 to 4 carbon atoms such as vinyl acetate
  • (meth)acrylates of alcohols having 1 to 4 carbon atoms such as methyl (meth)acrylate
  • Especially preferred comonomers are butyl acrylate, ethyl acrylate and methyl acrylate. Two or more such olefinically unsaturated compounds may be used in combination.
  • (meth)acrylic acid is intended to embrace both acrylic acid and methacrylic acid.
  • the polar group containing monomer units are selected from the group of acrylates and/or acetates.
  • the amount of polar group containing monomer units in the polyolefin preferably is 40 wt.% or less, more preferably 35 wt.% or less, and still more preferably is between 3 and 20 wt.%. Furthermore, preferably the polar group containing monomer units are present in the polyolefin in an amount of from 2.5 to 15 mol%, more preferably 3 to 10 mol%, and most preferably 3.5 to 6 mol%.
  • the cross-linkable polyolefin with hydrolysable silane groups (A) at the same time also contains the polar groups in any of the embodiments as described hereinbefore, i.e. the polyolefin is a terpolymer containing both the silane groups and the polar groups.
  • the preferred amounts for the silane group and the polar group containing monomers as described above apply for the terpolymer.
  • Such terpolymers may be produced by grafting, or, preferably, by copolymerisation of olefin monomers and unsaturated monomers containing silane groups and polar groups.
  • terpolymer containing both the silane groups and the polar groups is used in the composition of the invention, it is preferred that it makes up at least 80 wt.% of the total composition, more preferably at least 85 wt.%, and most preferably at least 90 wt.%.
  • a silanol condensation catalyst For cross-linking of such polyolefins, a silanol condensation catalyst must be used.
  • Conventional catalysts are for example tin-organic compounds such as dibutyl tin dilaurate (DBTDL).
  • DBTDL dibutyl tin dilaurate
  • acidic silanol condensation catalysts In contrast to the conventional tin-organic catalysts the acidic catalysts allow cross-linking to quickly take place already at room temperature.
  • acidic silanol condensation catalysts are disclosed for example in WO 95/17463. The contents of this document is enclosed herein by reference.
  • Examples for acidic silanol condensation catalysts comprise Lewis acids, inorganic acids such as sulphuric acid and hydrochloric acid, and organic acids such as citric acid, stearic acid, acetric acid, sulphonic acid and alkanoric acids as dodecanoic acid.
  • Preferred examples for a acidic silanol condensation catalyst are sulphonic acid and tin organic compounds.
  • the acidic silanol condensation catalyst comprises a sulfonic acid, preferably comprises an organic sulfonic acid.
  • the acidic silanol condensation catalyst comprises a sulphonic acid compound according to formula (V)
  • Ar being an aryl group with one or several aromatic rings, preferably 1 to 3 aromatic rings, more preferably 1 to 2 aromatic rings which may be substituted or non-substituted, and x being at least 1.
  • the acidic silanol condensation catalyst may comprise the structural unit according to formula (V) one or several times, e.g. two or three times.
  • two structural units according to formula (V) may be linked to each other via a bridging group such as an alkylene group.
  • the Ar group is an aryl group which is substituted with at least one C 1 - to C 30 -hydrocarbyl group, more preferably C 4 to C 30 -alkyl group.
  • the compound used as organic aromatic sulphonic acid silanol condensation catalyst has from 10 to 200 C-atoms, more preferably from 14 to 100 C-atoms.
  • the hydrocarbyl group is an alkyl substituent having 10 to 18 carbon atoms and still more preferred that the alkyl substituent contains 12 carbon atoms and is selected from dodecyl and tetrapropyl. Due to commercial availability it is most preferred that the aryl group is a benzene substituted group with an alkyl substituent containing 12 carbon atoms.
  • the currently most preferred compounds of formula (V) are dodecyl benzene sulphonic acid and tetrapropyl benzene sulphonic acid.
  • the acidic silanol condensation catalyst may also be precursor of a compound of formula (V), i.e. a compound that is converted by hydrolysis to a compound of formula (V).
  • a precursor is for example the acid anhydride of the sulphonic acid compound of formula (V).
  • a sulphonic acid of formula (V) that has been provided with a hydrolysable protective group as e.g. an acetyl group which can be removed by hydrolysis to give the sulphonic acid of formula (V).
  • the acidic silanol condensation catalyst is preferably used in an amount from
  • the preferred amount of acidic silanol condensation catalyst is from 0.001 to 2 wt% and more preferably 0.005 to 1 weight% based on the amount of acidic silanol groups containing polyolefin in the polymer composition used for the outer and/or insulation layer.
  • the effective amount of catalyst depends on the molecular weight of the catalyst used. Thus, a smaller amount is required of a catalyst having a low molecular weight than a catalysts having a high molecular weight.
  • the polymer composition according to the invention may further contain various additives, such as miscible thermoplastics, antioxidants, further stabilizers e.g. water tree retardants, scorch retardants, lubricants, fillers, colouring agents and foaming agents.
  • additives such as miscible thermoplastics, antioxidants, further stabilizers e.g. water tree retardants, scorch retardants, lubricants, fillers, colouring agents and foaming agents.
  • the total amount of additives is generally 0.3 to 10.0 wt.%, preferably 1.0 to 7.0 wt.%, more preferably 1.0 to 5.0 wt.%.
  • antioxidant preferably a compound, or a mixture of such compounds, is used which is neutral or acidic, must comprise a sterically hindered phenol group or aliphatic sulphur groups.
  • Such compounds are disclosed in EP 1 254 923 to be particularly suitable antioxidants for stabilisation of polyolefins containing hydrolysable silane groups which are crosslinked with a silanol condensation catalyst, in particular an acidic silanol condensation catalyst.
  • Other preferred antioxidants are disclosed in WO2005003199A1 .
  • the antioxidant is present in the composition in an amount of from 0.01 to 3.0 wt.%, more preferably 0.05 to 2.0 wt.%, and most preferably 0.08 to 1.5 wt.%.
  • filler preferably carbon black in an amount of 3.0 wt% or less, preferably 2.5 wt% or less, most preferably 2.0 wt% or less is used.
  • colouring agent all colouring agents apart from carbon black suitable for cable or pipe applications are used.
  • the at least one UV stabilizer (C) and optionally further additives may be compounded with the silane group containing polyolefin.
  • the at least one UV stabilizer (C) is usually added together with the acidic silanol condensation catalyst (B) to the silane group containing polyolefin by compounding the polymer with a so-called master batch, in which the catalyst, usually the at least one UV stabilizer (C), and optionally further additives are contained in a polymer, e.g. polyolefin, matrix in concentrated form.
  • the present invention also pertains to a master batch for a cross-linkable polyolefin composition comprising a matrix polymer and a acidic silanol condensation catalyst (B) in any of the above described embodiments.
  • the matrix polymer is preferably a polyolefin, more preferably a polyethylene, which may be a homo- or copolymer of ethylene, e.g. low density polyethylene, or polyethylene-methyl-, -ethyl, or -butyl-acrylate copolymer containing 1 to 50 wt.% of the acrylate, and mixtures thereof.
  • a polyolefin more preferably a polyethylene, which may be a homo- or copolymer of ethylene, e.g. low density polyethylene, or polyethylene-methyl-, -ethyl, or -butyl-acrylate copolymer containing 1 to 50 wt.% of the acrylate, and mixtures thereof.
  • the compounds to be added to the silane group containing polyolefin and the at least one UV stabilizer (C) are contained in concentrated form, i.e. in a much higher amount than in the final composition.
  • the master batch preferably comprises component (B) in an amount of from 0.3 to 15 wt.%, more preferably from 0.7 to 10 wt.%.
  • the master batch also contains some or all of the other additives as described above, for example the stabilizers.
  • amount of the stabilizers contained in the master batch is up to 20 wt.%.
  • the master batch preferably is compounded with the silane group containing polymer and the at least one UV stabilizer (C) in an amount of from 1 to 10 wt.%, more preferably from 2 to 8 wt.%.
  • Compounding may be performed by any known compounding process, including extruding the final product with a screw extruder or a kneader.
  • the polyolefin compositions according to all aspects of the present invention preferably show excellent curing properties in the ice test represented by an amount of ⁇ F of more than 40 Nm, more preferably more than 43 Nm, most preferably more than 45 Nm.
  • polyolefin compositions according to all aspects of the present invention preferably show excellent cross-linking properties in the ice test represented by a high cross-linking speed of more than 0.10 Nm/s, more preferably more than 0.1 1 Nm/s, most preferably more than 0.12 Nm/s.
  • the polyolefin compositions according to all aspects of the present invention preferably show improved UV resistance as can be seen in a retention of more than 60 %, more preferably more than 70 %, most preferably more than 75 % of the elongation at break after 500 h in SEPAP UV exposure.
  • the present invention furthermore relates to a article, comprising the polyolefin composition in any of the above described embodiments.
  • the article refers to a wire or cable or a pipe preferably used or stored outdoors.
  • the article refers to a coloured cable.
  • the article refers to a natural coloured cable, which includes cables coloured by any of the pigments or pigment masterbatches intended to be used with polyolefins as a colouring agent.
  • the invention relates to a medium or high voltage cable comprising one or more conductors in a cable core, an inner semiconducting layer, followed by an insulating layer, and then an outer semiconducting layer, and an outer protective jacket wherein at least one of these layers, preferably the outer layer or the insulating layer when the outer layers are pealed off, comprises the polyolefin composition as described above.
  • Insulating layers for medium or high voltage power cables generally have a thickness of at least 2 mm, typically at least 2.3 mm, and the thickness increases with increasing voltage the cable is designed for.
  • the insulating layer has a thickness of at least 4 mm, more preferably at least 5 mm. This corresponds to a 10 kV and a 20 kV cable, respectively.
  • semiconductive and insulating layers may be present in medium or high voltage cables, such as a metallic tape or wire shield, and, finally, an outermost jacketing layer.
  • the invention relates to a low voltage cable comprising one or more conductors in a cable core followed by an insulating layer and an outer protective jacket wherein at least one of these layers, preferably the outer layer or the insulating layer when the outer layers are pealed off, comprises the polyolefin composition as described above.
  • the cable is produced by co-extrusion of the different layers onto the conducting core. Then, cross-linking is performed by moisture curing, wherein in the presence of the acidic silanol condensation catalyst the silane groups are hydrolysed under the influence of water or steam, resulting in the splitting off of alcohol and the formation of silanol groups, which are then cross-linked in a condensation reaction wherein water is split off.
  • Moisture curing may be performed in a sauna or water bath at temperatures of 70 to 100 0 C.
  • the curing is performed at temperature of 5 to 50 C C, more preferably of 10 to 40 0 C and a humidity below 85 %, more preferably below 75 %.
  • the invention relates furthermore to the use of the polyolefin composition in any of the above described embodiments for the production of an article, preferably a layer of a wire or cable, more preferably of a layer, still more preferably an insulating layer, of a medium or high voltage cable.
  • the invention relates furthermore to the use of the polyolefin composition in any of the above described embodiments for the production of a layer of low voltage cables, more preferably of a jacketing layer for outdoor low voltage cables and of an insulation layer for indoor low voltage cables.
  • the invention relates furthermore to the use of the polyolefin composition in any of the above described embodiments for the production of a layer of a cable, preferably of a track resistant cable mounted in power lines.
  • the melt flow rate is determined according to ISO 1 133 and is indicated in g/10 min.
  • the MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.
  • the MFR is determined at 190 0 C for polyethylenes and may be determined at different loadings such as 2.16 kg (MFR 2 ) or 21.6 kg (MFR 21 ).
  • the MFR is determined at 230 0 C for polypropylenes.
  • the ice test refers to an internal measurement method. The purpose of this measurement is to determine the cross-linking speed of silane group containing polyolefins by curing the polyolefin at 120 0 C in a Brabender mixer with rotors, a volume of 287 cm 3 and a recorder for time, temperature and torque by adding catalyst and ice.
  • the weights and volumes of the components are calculated to have 254 cm 3 .
  • the chamber temperature is set to 120 0 C and it is checked that the temperature is stable.
  • the polymer resin is charged into the chamber in portions. When the resin is melted, the additives which are not part of the catalyst masterbatch are added. After dispersion of the additives in the melt, the catalyst masterbatch is charged. The melt is further mixed until the torque baseline is stable.
  • crushed ice made from deionised water and packed in a small polyethylene plastic bag, is added to the melt and the time, temperature and torque are recorded until the cure is completed or for a maximum time of 2 h.
  • ⁇ F [Nm] is calculated from maximum torque recorded subtracted by the minimum torque which represents the baseline when adding the ice.
  • the cross-linking speed [Nm/s] is calculated from ⁇ F divided by the time in seconds it takes from adding the ice to reaching the maximum torque.
  • test method B 1 has been utilized.
  • a matrix resin an ethylene butylacrylate copolymer with 17 wt.% butylacrylate, a density of 926 kg/m 3 and a MFR 2 of 0.9 g/10 min;
  • DBSA dodecylbenzenesulfonic acid
  • HDTMS hexadecyltrimethoxysilane
  • the masterbatch of Table 1 was compounded in an amount of 5 wt.% with 94.6 wt.% of a silane group containing polyethylene having a density of 923 kg/m 3 , a MFR 2 of 1 g/10 min and a silane copolymer content of 1.9 wt.% and 0.4 wt% of an UV stabilizer as listed in Table 2 in a Brabender kneader to yield the compositions for the insulating layer of a power cable (inventive Examples Ex1 to Ex5, comparative Examples CE1 to CE5).
  • Example CE6 For a further comparative Example CE6 the master batch of Table 1 was compounded in an amount of 5 wt.% with 94.75 wt.% of the above silane group containing polyethylene and 0.25 wt% of an UV stabilizer as listed in Table 2 in a Brabender kneader. In Example Ex6 0.2 wt% of UV stabilizer as listed in Table 2 was compounded with the masterbatch in an amount of 5 wt.% and with 94.8 wt.% of the above silane group containing polyethylene. Table 2:
  • Tinuvin ® 622, Tinuvin ® 327, Tinuvin ® 120 and Tinuvin ® 326 are distributed by Ciba
  • Uvinul ® 3028, Uvinul ® 3029 and Uvinul ® 3034 are distimped by BASF
  • Hostavin ® ARO 8 and Sanduvor ® VSU are distributed by Clariant
  • ADK stab LA-31 and LA-81 are distributed by Adeka-Palmarole.
  • the cure of the compositions Ex1 to Ex6 and CE1 to CE5 is measured as torque increase in the ice test and reported as ⁇ F which represents F n - F start . Further the cross-linking speed is determined from ⁇ F.
  • inventive polyolefin compositions prove good cure properties of at least 46.9 Nm and a cross-linking speed of at least 0.13 Nm/s.
  • comparative Example CE6 which has a pH of 6.3 no cross-linking and almost no curing occurs.
  • dogbones from tape of the polymer compositions Ex1 and CE1 to CE5 were produced, exposed to UV light for 400 h, 500 h, 1000 h, 2000 h or 3000 h and afterwards tested for the breaking stress and the elongation at break.
  • the results of the tests are given in Table 4 as regards the breaking stress and in Table 5 as regards the elongation at break after exposure to UV light for 400 h, 500 h, 1000 h, 2000 h or 3000 h.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention porte sur une composition de polyoléfine comprenant (A) une polyoléfine réticulable avec des groupes silanes hydrolysables (B) et un catalyseur de condensation des silanols, caractérisée par le fait que le Δ F est de plus de 40 Nm, la vitesse de réticulation est de plus de 0,1 Nm/s dans le test de la glace et la rétention est de plus de 60 % de l'allongement à la rupture après 500 h d'exposition aux UV SEPAP. L'invention porte également sur une composition de polyoléfine comprenant (A) une polyoléfine réticulable avec des groupes silanes hydrolysables (B) un catalyseur acide de condensation des silanols acides, et (C) au moins un stabilisant vis-à-vis des UV qui est acide, à savoir qui a un pH égal ou inférieur à 6,2, mesuré à 20-25 °C et avec une suspension à 1 % en poids l'invention porte également sur un article comprenant une telle composition et sur l'utilisation d'une telle composition pour la production d'un article.
PCT/EP2008/010653 2007-12-20 2008-12-15 Stabilisation vis-à-vis des uv d'une composition de polyoléfine réticulable comprenant un catalyseur acide de condensation des silanols acides WO2009080235A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2008801217386A CN101903451B (zh) 2007-12-20 2008-12-15 一种包含酸性硅烷醇缩合催化剂的可交联的聚烯烃组合物的uv稳定化方法
US12/809,569 US20100267869A1 (en) 2007-12-20 2008-12-15 Uv stabilization of a cross-linkable polyolefin composition comprising an acidic silanol condensation catalyst
BRPI0821163A BRPI0821163B1 (pt) 2007-12-20 2008-12-15 composição de poliolefina reticulável compreendendo um catalisador de condensação de silanol ácido, artigo e uso de uma composição de poliolefina

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07024836.4 2007-12-20
EP07024836A EP2072568B1 (fr) 2007-12-20 2007-12-20 Stabilisation par UV d'une composition de polyoléfine réticulable comprenant un catalyseur de condensation au silanol acide

Publications (1)

Publication Number Publication Date
WO2009080235A1 true WO2009080235A1 (fr) 2009-07-02

Family

ID=39370442

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/010653 WO2009080235A1 (fr) 2007-12-20 2008-12-15 Stabilisation vis-à-vis des uv d'une composition de polyoléfine réticulable comprenant un catalyseur acide de condensation des silanols acides

Country Status (7)

Country Link
US (1) US20100267869A1 (fr)
EP (1) EP2072568B1 (fr)
CN (1) CN101903451B (fr)
AT (1) ATE536387T1 (fr)
BR (1) BRPI0821163B1 (fr)
PL (1) PL2072568T3 (fr)
WO (1) WO2009080235A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT2508566E (pt) * 2011-04-07 2014-07-09 Borealis Ag Composição de polímero de ligação cruzada com silano
CN102682871B (zh) * 2012-05-28 2014-03-26 四川大学 一种电力电缆绝缘老化的自由基清除剂及其自动愈合方法
KR20210005655A (ko) * 2018-04-27 2021-01-14 다우 글로벌 테크놀로지스 엘엘씨 광안정제를 함유하는 중합체 조성물
CA3143366A1 (fr) * 2019-06-27 2020-12-30 Dow Global Technologies Llc Procede de fabrication d'un melange homogene de polyolefine et d'acide organique liquide
EP3778746A1 (fr) * 2019-08-14 2021-02-17 Borealis AG Stabilisation uv d'une composition de polyoléfine réticulable comprenant un catalyseur de condensation de silanol acide
EP3778747A1 (fr) * 2019-08-14 2021-02-17 Borealis AG Stabilisation uv d'une composition de polyoléfine réticulable comprenant un catalyseur de condensation de silanol acide
EP4025641A4 (fr) * 2019-09-06 2023-05-31 Dow Global Technologies LLC Composition polymère réticulable et conducteur revêtu
CN118891310A (zh) * 2022-03-24 2024-11-01 北欧化工公司 聚合物组合物及其作为硅烷醇缩合催化剂母料的应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000058975A1 (fr) * 1999-03-25 2000-10-05 Ciba Specialty Chemicals Holding Inc. Composition stabilisee d'isolement de cables de telecommunications
US6232376B1 (en) * 1999-10-14 2001-05-15 Nippon Unicar Company Ltd. Moisture curable polyolefin compositions
EP1201827A1 (fr) * 2000-10-23 2002-05-02 Borealis Technology Oy Poteau pour barrière de sécurité routière
US20030050401A1 (en) * 2000-11-06 2003-03-13 Peter Jackson Crosslinked, predominantly polypropylene-based compositions
US20030096904A1 (en) * 2000-07-25 2003-05-22 Takashi Hakuta Curable composition and its use
EP1433811A2 (fr) * 2001-05-02 2004-06-30 Borealis Technology Oy Ultilisation de Polysulfides pour la stabilisation de polymères réticulés contenant des groupes silanes
EP1760111A1 (fr) * 2005-08-31 2007-03-07 Borealis Technology Oy Composition de polyoléfine contenant un catalyseur de condensation de silanol décolorer-libre
EP1834987A1 (fr) * 2006-03-15 2007-09-19 Borealis Technology Oy Composition à base de polypropylène ayant une phase dispersée selectivement réticulable

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE794718Q (fr) 1968-12-20 1973-05-16 Dow Corning Ltd Procede de reticulation d'olefines
GB1526398A (en) 1974-12-06 1978-09-27 Maillefer Sa Manufacture of extruded products
US4413066A (en) 1978-07-05 1983-11-01 Mitsubishi Petrochemical Company, Ltd. Crosslinkable polyethylene resin compositions
JPS5566809A (en) 1978-11-13 1980-05-20 Mitsubishi Petrochemical Co Method of manufacturing crosslinked polyethylene resinncoated wire
JPS5693542A (en) 1979-12-27 1981-07-29 Mitsubishi Petrochemical Co Bridged polyethylene resin laminated film or sheet
JPS5695940A (en) 1979-12-28 1981-08-03 Mitsubishi Petrochem Co Ltd Ethylene polymer composition
JPS57207632A (en) 1981-06-16 1982-12-20 Mitsubishi Petrochem Co Ltd Crosslinkable polyethylene resin composition
JPS5861129A (ja) 1981-10-08 1983-04-12 Sekisui Plastics Co Ltd 発泡体の製造法
SE502171C2 (sv) 1993-12-20 1995-09-04 Borealis Holding As Polyetenkompatibla sulfonsyror som silanförnätningskatalysatorer
US6337367B1 (en) 2000-07-11 2002-01-08 Pirelli Cables And Systems, Llc Non-shielded, track resistant, silane crosslinkable insulation, methods of making same and cables jacketed therewith
JP2003192846A (ja) 2001-12-26 2003-07-09 Furukawa Electric Co Ltd:The 耐熱性・耐候性に優れた絶縁樹脂組成物および絶縁電線
CN1500836A (zh) 2002-11-18 2004-06-02 华昌工贸有限公司 聚碳酸酯(pc)塑木板材
EP1641850A1 (fr) 2003-06-25 2006-04-05 Union Carbide Chemicals & Plastics Technology Corporation Composition polymere reticulable a l'humidite contenant des antioxydants speciaux
CN100487061C (zh) * 2003-09-02 2009-05-13 株式会社钟化 固化性组合物
EP1731508B1 (fr) * 2004-03-02 2012-08-01 Adeka Corporation Amines striquement encombres faiblement basiques comportant des structures de carbonate, compositions de resines synthetiques et positions de revetement
US20070203297A1 (en) * 2004-04-01 2007-08-30 Kaneka Corporation Curable Composition
US20090088513A1 (en) * 2005-06-29 2009-04-02 Adeka Corporation Resin additive composition and resin composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000058975A1 (fr) * 1999-03-25 2000-10-05 Ciba Specialty Chemicals Holding Inc. Composition stabilisee d'isolement de cables de telecommunications
US6232376B1 (en) * 1999-10-14 2001-05-15 Nippon Unicar Company Ltd. Moisture curable polyolefin compositions
US20030096904A1 (en) * 2000-07-25 2003-05-22 Takashi Hakuta Curable composition and its use
EP1201827A1 (fr) * 2000-10-23 2002-05-02 Borealis Technology Oy Poteau pour barrière de sécurité routière
US20030050401A1 (en) * 2000-11-06 2003-03-13 Peter Jackson Crosslinked, predominantly polypropylene-based compositions
EP1433811A2 (fr) * 2001-05-02 2004-06-30 Borealis Technology Oy Ultilisation de Polysulfides pour la stabilisation de polymères réticulés contenant des groupes silanes
EP1760111A1 (fr) * 2005-08-31 2007-03-07 Borealis Technology Oy Composition de polyoléfine contenant un catalyseur de condensation de silanol décolorer-libre
EP1834987A1 (fr) * 2006-03-15 2007-09-19 Borealis Technology Oy Composition à base de polypropylène ayant une phase dispersée selectivement réticulable

Also Published As

Publication number Publication date
PL2072568T3 (pl) 2012-05-31
BRPI0821163B1 (pt) 2018-11-06
ATE536387T1 (de) 2011-12-15
US20100267869A1 (en) 2010-10-21
BRPI0821163A2 (pt) 2015-06-16
CN101903451A (zh) 2010-12-01
EP2072568A1 (fr) 2009-06-24
EP2072568B1 (fr) 2011-12-07
CN101903451B (zh) 2012-11-21

Similar Documents

Publication Publication Date Title
EP2072568B1 (fr) Stabilisation par UV d'une composition de polyoléfine réticulable comprenant un catalyseur de condensation au silanol acide
EP1862501B1 (fr) Un composé de silicium comme un auxiliaire de traitement dans les compositions polyolefiniques comprenant des polyoléfines avec des groupes de silanes hydrolisables
EP2207845B1 (fr) Câble électrique comprenant une composition polyoléfinique réticulable comprenant du dicarboxylate de dihydrocarbyl-étain comme catalyseur de condensation de silanol
KR102612380B1 (ko) 플렉시블 케이블용 수분 경화성 중합체
US8529815B2 (en) Polyolefin composition comprising crosslinkable polyolefin with silane groups, silanol condensation catalyst and silicon containing compound
EP2251365B1 (fr) Composition de polyoléfine réticulable comportant des groupes de silanes formant un acide ou une base par une hydrolisation
WO2010130458A1 (fr) Composition de polyoléfine pouvant être réticulée comprenant des groupes silane formant un acide ou une base après hydrolyse
KR102695577B1 (ko) 산성 실라놀 축합 촉매를 포함하는 가교성 폴리올레핀 조성물의 uv 안정화
KR102698648B1 (ko) 산성 실란올 축합 촉매를 포함하는 가교성 폴리올레핀 조성물의 uv 안정화
EP1862500B2 (fr) Composé contenant du silicium de dessication pour des compositions polyoléfines
EP4169976A1 (fr) Composition de polyéthylène pour isolations de câbles présentant une meilleure stabilité uv
EP4201985A1 (fr) Composition polymère adaptée à l'isolation des câbles
BR112022002231B1 (pt) Composição de poliolefina, artigo e uso de uma composição de poliolefina

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200880121738.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08864789

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2047/KOLNP/2010

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: MX/A/2010/006609

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 12809569

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08864789

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: PI0821163

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20100618